US9702024B2ActiveUtilityA1

Method for the hydrometallurgical recovery of lithium, nickel and cobalt from the lithium transition metal oxide-containing fraction of used galvanic cells

86
Assignee: Rockwood Lithium GmbHPriority: Oct 10, 2012Filed: Oct 9, 2013Granted: Jul 11, 2017
Est. expiryOct 10, 2032(~6.3 yrs left)· nominal 20-yr term from priority
Inventors:David WohlgemuthMark Andre SchneiderRebecca SpielauJohannes WillemsMartin Steinbild
H01M 10/54C01G 53/42C22B 7/007C01B 25/45C22B 26/12C22B 23/043C01G 51/42C01P 2006/40Y02W30/84C22B 23/0461Y02P10/20Y02P10/234
86
PatentIndex Score
10
Cited by
11
References
28
Claims

Abstract

A method for the hydrometallurgical recovery of lithium from a lithium transition metal oxide containing fraction of used galvanic cells is disclosed. According to the method, the lithium transition metal oxide containing fraction is introduced into sulphuric acid or hydrochloric acid, and hydrogen peroxide is added in an amount that is at least stoichiometric relative to the transition metal content to be reduced of the lithium transition metal oxide-containing fraction.

Claims

exact text as granted — not AI-modified
The invention claimed is: 
     
       1. A method for hydrometallurgical recovery of lithium, nickel, and cobalt from a fraction of used galvanic cells containing lithium transition metal oxides comprising the steps of:
 introducing a fraction containing lithium transition metal oxides, wherein the transition metals are nickel, cobalt and/or manganese, having an aluminum content up to 5 wt. % and a particle size up to 500 μm into sulphuric acid having a concentration of 0.5 to 4 mol/l in an amount that is at least stoichiometric relative to the oxide content of the fraction containing lithium transition metal oxides and in a liquid/solid ratio in a range of 20 to 250 g/l; 
 solubilizing the lithium contained in the fraction containing lithium transition metal oxides with addition of at least a stoichiometric amount of hydrogen peroxide relative to the transition metal content of the fraction containing lithium transition metal oxide at temperatures of 35 to 70° C., wherein a solution containing lithium sulphate and sulphates of the transition metals is formed; 
 separating the lithium sulphate and the sulphates of the transition metals from a remaining residue; and 
 washing the remaining residue at least twice, wherein a washing solution containing lithium sulphate-containing washing solution is formed; 
 wherein the separated lithium sulphate and the lithium sulphate-containing washing solution are combined, 
 wherein the transition metals are precipitated as hydroxides in the pH range of 9 to 11, and the transition metals are separated and washed, and 
 wherein the combined lithium sulphate and the lithium sulphate-containing washing solution is converted by means of electrodialysis with bipolar membranes into lithium hydroxide. 
 
     
     
       2. A method according to  claim 1 , wherein a fraction containing lithium transition metal oxide is used having an aluminum content up to 3 wt. %. 
     
     
       3. A method according to  claim 1 , wherein a content of multivalent cations is reduced by means of an ion exchanger. 
     
     
       4. A method according to  claim 1 , wherein the fraction containing the lithium transition metal oxide has a particle size up to 100 to 400 μm. 
     
     
       5. A method according to  claim 1 , wherein the sulphuric acid is used at a concentration of 0.75 to 2.5 mol/l. 
     
     
       6. A method according to  claim 1 , wherein the solid/liquid ratio is adjusted in the range of 30 to 230 g/l. 
     
     
       7. A method according to  claim 1 , wherein the solubilizing step is carried out at temperatures of 35 to 65° C. 
     
     
       8. A method according to  claim 1 , wherein the remaining residue is washed at least three times. 
     
     
       9. A method according to  claim 1 , wherein the sulphuric acid and/or the hydrogen peroxide is used in excess. 
     
     
       10. A method according to  claim 9 , wherein an excess of 0.1 to 10 mol % of the sulphuric acid and/or the hydrogen peroxide is used. 
     
     
       11. A method for hydrometallurgical recovery of lithium, nickel, and cobalt from a fraction of used galvanic cells containing lithium transition metal oxides, comprising the steps of:
 introducing a fraction containing lithium transition metal oxides, wherein the lithium transition metal oxides are oxides comprising nickel, cobalt and/or aluminum, having a particle size up to 500 μm into sulphuric acid having a concentration of 0.5 to 4 mol/l in an amount that is at least stoichiometric relative to the oxide content of the fraction containing lithium transition metal oxide and in a liquid/solid ratio in the range of 20 to 300 g/l; 
 solubilizing the lithium contained in the fraction containing lithium transition metal oxides with addition of at least a stoichiometric amount of hydrogen peroxide relative to the transition metal content of the fraction containing lithium mixed oxide at temperatures of 35 to 70° C., wherein a solution containing lithium sulphate and sulphates of the transition metals is formed; 
 separating the lithium sulphates and sulphates of the transition metals from a remaining residue, and 
 washing the remaining residue at least twice, wherein a lithium sulphate-containing washing solution is formed, and 
 wherein the separated lithium sulphate and the lithium sulphate-containing washing solution are combined, 
 wherein the transition metals are precipitated as hydroxides in the pH range of 9 to 11, and the transition metals are separated and washed, and 
 wherein the combined lithium sulphate and the lithium sulphate-containing washing solution is converted into lithium hydroxide by means of electrodialysis with bipolar membranes. 
 
     
     
       12. A method according to  claim 11 , wherein a content of multivalent cations is reduced by means of an ion exchanger. 
     
     
       13. A method according to  claim 11 , wherein the fraction containing the lithium transition metal oxide has a particle size up to 100 to 400 μm. 
     
     
       14. A method according to  claim 11 , wherein the sulphuric acid is used at a concentration of 0.75 to 2.5 mol/l. 
     
     
       15. A method according to  claim 11 , wherein the solid/liquid ratio is in the range of 50 to 250 g/l. 
     
     
       16. A method according to  claim 11 , wherein the solubilizing step is carried out at temperatures of 35 to 65° C. 
     
     
       17. A method according to  claim 11 , wherein the remaining residue is washed at least three times. 
     
     
       18. A method according to  claim 11 , wherein the sulphuric acid and/or the hydrogen peroxide is used in excess. 
     
     
       19. A method according to  claim 18 , wherein an excess of 0.1 to 10 mol % of the sulphuric acid and/or the hydrogen peroxide is used. 
     
     
       20. A method for hydrometallurgical recovery of lithium, nickel, and cobalt from a lithium mixed-oxide-containing fraction of used galvanic cells, comprising the steps of introducing a fraction containing lithium transition metal oxides, wherein the lithium transition metal oxides are metal oxides of nickel, cobalt and/or aluminum, having a particle size up to 500 μm into hydrochloric acid having a concentration of 0.5 to 4 mol/l in an amount that is at least stoichiometric relative to the oxide content of the fraction containing lithium transition metal oxides, and in a solid/liquid ratio in the range of 10 to 150 g/l;
 solubilizing the lithium contained in the fraction containing lithium transition metal oxides with addition of at least a stoichiometric amount of hydrogen peroxide with respect to the transition metal content of the fraction containing lithium metal oxides at temperatures of 35 to 70° C., wherein a solution containing lithium chloride and chlorides of the transition metals is formed; 
 separating the lithium chloride and chlorides of the transition metals from a remaining residue, and 
 washing the remaining residue at least twice to form a metal chloride-containing wash-solution, and 
 wherein the separated lithium chloride and chlorides of the transition metals and the metal chloride-containing wash-solution are combined, 
 wherein the transition metals are precipitated in the pH range of 9 to 11 as hydroxides, and the transition metals are separated and washed, and 
 wherein the combined lithium chloride and metal chloride-containing wash solution is converted by electrodialysis with bipolar membranes into lithium hydroxide. 
 
     
     
       21. A method according to  claim 20 , wherein a content of multivalent cations is reduced by means of an ion exchanger. 
     
     
       22. A method according to  claim 20 , wherein the fraction containing the lithium transition metal oxide has a particle size up to 100 to 400 μm. 
     
     
       23. A method according to  claim 20 , wherein the hydrochloric acid is used at a concentration of 0.75 to 2.5 mol/l. 
     
     
       24. A method according to  claim 20 , wherein the solid/liquid ratio is in the range of 15 to 120 g/l. 
     
     
       25. A method according to  claim 20 , wherein the solubilizing step is carried out at temperatures of 35 to 65° C. 
     
     
       26. A method according to  claim 20 , wherein the remaining residue is washed at least three times. 
     
     
       27. A method according to  claim 20 , wherein the hydrochloric acid and/or the hydrogen peroxide is used in excess. 
     
     
       28. A method according to  claim 27 , wherein an excess of 0.1 to 10 mol % of the hydrochloric acid and/or the hydrogen peroxide is used.

Cited by (0)

No later patents cite this yet.

References (0)

No backward citations on record.